US5629268A - Process for preparing a layered superconducting structure - Google Patents

Process for preparing a layered superconducting structure Download PDF

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Publication number
US5629268A
US5629268A US08/457,313 US45731395A US5629268A US 5629268 A US5629268 A US 5629268A US 45731395 A US45731395 A US 45731395A US 5629268 A US5629268 A US 5629268A
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superconductor layer
superconductor
oxide
deposited
set forth
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Expired - Fee Related
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US08/457,313
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English (en)
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So Tanaka
Takao Nakamura
Michitomo Iiyama
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority claimed from JP3089621A external-priority patent/JP2773456B2/ja
Priority claimed from JP3089620A external-priority patent/JP2773455B2/ja
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Priority to US08/457,313 priority Critical patent/US5629268A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0912—Manufacture or treatment of Josephson-effect devices
    • H10N60/0941—Manufacture or treatment of Josephson-effect devices comprising high-Tc ceramic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
    • Y10S505/701—Coated or thin film device, i.e. active or passive
    • Y10S505/702—Josephson junction present
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y10S505/73—Vacuum treating or coating
    • Y10S505/731—Sputter coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y10S505/73—Vacuum treating or coating
    • Y10S505/732—Evaporative coating with superconducting material

Definitions

  • the present invention relates to a process for preparing layered thin films, more particularly, it relates to a process for depositing a plurality of thin films including a bottom superconductor layer on a substrate successively to produce a layered superconducting structure.
  • Oxide superconductors are expected to be used in a variety of applications due to their higher critical temperatures than conventional metal superconductors.
  • Y--Ba--Cu--O oxide superconductor possess the critical temperature above 80K and Bi--Sr--Ca--Cu--O and Tl--Ba--Ca--Cu--O oxide superconductors possess that of above 100K.
  • oxide superconductors When the oxide superconductors are used in superconducting devices, it is indispensable to prepare a thin film of oxide superconductor and to laminate a plurality thin films including a bottom superconductor layer successively on a substrate.
  • a superconducting junction so-called tunnel type Josephson Junction realized with oxide superconductor, it is requested to deposit a bottom superconductor layer, an intermediate layer of non-superconductor and a top superconductor layer on a substrate successively in this order.
  • Josephson element is a two-terminals element, so that a logical circuit consisting of Josephson elements alone becomes complicated.
  • a variety of ideas of three-terminals elements are proposed.
  • the superconductor transistors consisting of superconductor and semiconductor which is a typical three-terminals element, it is also required to combine a thin film of semiconductor with a thin film of oxide superconductor and hence successive deposition of thin films each consisting of different material is required.
  • a superconducting current passes through a thin film of non-superconductor sandwiched between two adjacent layers of superconductors positioned close to each other.
  • a distance between the two adjacent superconductors is determined by the coherence length of superconductor. Since the coherence length of oxide superconductors is very short, the distance between two adjacent superconductors must be several nanometer.
  • all thin films in the superconducting device must have high crystallinity, in other words, these thin films are made preferably of a single crystal or polycrystal having crystal orientation which is similar to single crystal.
  • the superconducting device has thin film(s) made of polycrystal whose crystal orientation is not well-ordered or has amorphous thin film(s), high-performance of the superconducting device can not be expected and hence function thereof become unstable.
  • the surface condition of the bottom superconductor layer should be considered carefully because the coherence length of oxide superconductors is very short and hence the superconductivity is easily lost. Therefore, the surface of bottom superconductor layer must be clean and also must have well-ordered crystallinity or superconducting property.
  • constituent elements of the top superconductor layer diffuse or migrate into the bottom superconductor layer, resulting in that an interface between these layers becomes unclear and thin films of oxide superconductor are deteriorated.
  • An object of the present invention is to solve the problems and to provide a process for preparing layered thin films comprising a bottom superconductor layer and the other thin film layers deposited on the bottom superconductor layer and having improved crystallinity and continuity especially at superconducting interfaces.
  • the present invention provides a process for depositing successively a plurality of thin films on a bottom superconductor layer made of oxide superconductor deposited on a substrate, characterized in that deposition of all of the bottom superconductor layer and the thin films is carried out in a single chamber successively.
  • the deposition is carried out preferably under one of following conditions (1) and (2):
  • Deposition of a first thin film to be deposited directly on the bottom superconductor layer is effected under such condition that the bottom superconductor layer is heated above the oxygen-trap temperature (T trap ) at which oxygen enter into the oxide superconductor but lower than the film forming temperature of the bottom superconductor layer.
  • T trap oxygen-trap temperature
  • the bottom superconductor layer is heated in a ultra-high vacuum chamber at a temperature lower than the oxygen-trap temperature (T trap ) but higher than a temperature which is lower by 100° C. than the oxygen-trap temperature (T trap -100° C.), and then the first thin film is deposited on the bottom superconductor layer.
  • the oxygen-trap temperature (T trap ) and the film forming temperature are known for respective oxide superconductor.
  • the process according to the present invention is applicable to any known oxide superconductors and is advantageously applicable to Y--Ba--Cu--O oxide superconductor, Bi--Sr--Ca--Cu--O oxide superconductor and Tl--Ba--Ca--Cu--O oxide superconductor which have the most attractive properties including their high critical temperatures.
  • the substrate is preferably a single crystal of oxide such as MgO, StTiO 3 , PrGaO 3 or the like.
  • a layered structure containing at least one thin film of oxide superconductor of high quality can be produced under one of the conditions (1) and (2).
  • deposition of the bottom and top superconductor layers and an oxygen-containing thin film to be deposited on the bottom superconductor layer is carried out in an atmosphere of oxygen having the purity of higher than 5N (99.999%).
  • oxygen having the purity of higher than 5N (99.999%).
  • Existence of H 2 O and CO 2 in oxygen deteriorate the oxide, superconductor because they react easily with the oxide superconductor so that H 2 O and CO 2 should be eliminated as small as possible.
  • the bottom superconductor layer is a c-axis oriented thin film of Y 1 Ba 2 Cu 3 O 7-x
  • the first thin film is made of non-superconductor, for example oxide such as MgO or metal such as Ag and a second thin film to be deposited on the first thin film is a top superconductor layer of Y 1 Ba 2 Cu 3 O 7-x .
  • deposition of all thin films to be deposited on the bottom superconductor layer is effected at a substrate temperature between 400° and 600° C. under the deposition of condition (1), and the bottom superconductor layer is heated in ultra-high vacuum of lower than 1 ⁇ 10 -9 Torr at the substrate temperature between 350° and 400° C. before the first thin film is deposited under the condition (2).
  • the first thin film When deposition of the first thin film is carried out in the temperature range defined by the condition (1), enough oxygen enter into the oxide superconductor and diffusion of constituent elements of the first thin film into the bottom superconductor layer can be prevented effectively.
  • the bottom superconductor layer is a thin film of Y--Ba--Cu--O oxide superconductor
  • the first thin film of MgO or Ag is deposited at the substrate temperature between 400° and 600° C.
  • the first thin film When deposition of the first thin film is carried out in the temperature range defined by the condition (2), oxygen do not escape out of the bottom superconductor layer and constituent elements of the thin film deposited directly on the bottom superconductor layer do not diffuse or migrate into the bottom superconductor layer.
  • the bottom superconductor layer is a thin film of Y--Ba--Cu--O oxide superconductor
  • the first thin film of MgO or Ag is deposited at the substrate temperature between 350° and 400° C.
  • the process according to the present invention characterized by the condition (1) and (2) is useful for fabricating a superconducting element comprising a bottom superconductor layer, an intermediate layer made of insulator or ordinary conductor and a top superconductor layer having a different crystal orientation.
  • all layers of bottom superconductor layer and thin films deposited thereon must be produced successively in a single chamber so that the bottom superconductor layer does not contact with air and hence a surface of the bottom superconductor layer is neither contaminated nor deteriorated by a reaction with moisture in air.
  • the stratified thin films prepared by the process according to the present invention show improved crystallinity and continuity especially at superconducting interfaces which are requested for realizing superconducting elements or integrated superconducting circuits so that high-performance superconducting systems can be realized.
  • FIGS. 1A, 1B, 1C and 1D illustrate successive steps for preparing a layered structure containing at least one thin film of oxide superconductor by the process according to the present invention.
  • FIG. 1A shows a substrate (5) on which thin films are to be deposited successively by the process according to the present invention.
  • a bottom superconductor layer (1) is deposited on the substrate (5) preferably in an atmosphere of high-pure oxygen by off-axis sputtering method, laser abrasion method, reaction evaporation method, MBE or CVD technique (FIG. 1B).
  • the chamber is evacuated under a background pressure of lower than 1 ⁇ 10 -9 Torr and the temperature of bottom superconductor layer (1) is adjusted within the range determined by the present invention.
  • a first thin film (2) such as a thin film of MgO or Ag is deposited by sputtering method, laser abrasion method, evaporation method, MBE or CVD technique or the like (FIG. 1C) under the conditions determined by the present invention.
  • a second thin film (3) such as a top superconductor layer is deposited by off-axis sputtering method, laser abrasion method, reaction evaporation method, MBE or CVD technique (FIG. 1D) under the conditions determined by the present invention.
  • a substrate (5) of MgO (100) is placed in a ultra-high vacuum chamber which is then evacuated to 1 ⁇ 10 -9 Torr.
  • Substrate temperature 700° C.
  • a thin film of oxide superconductor of Y 1 Ba 2 Cu 3 O 7-x (3) having a thickness of 200 nm is deposited on the resulting thin film of MgO (2).
  • Deposition of this top superconductor layer (3) can be carried out by the same method as above but the substrate temperature must be adjusted in a range between 400° and 600° C.
  • the off-axis sputtering is carried out under following operational conditions:
  • Substrate temperature 570° C.
  • Example 1 is repeated but the MgO thin film is replaced by a thin film of Ag of the same thickness.
  • Example 2 after deposition is complete, the substrate temperature is lowered to 500° C. and then a thin film of Ag is deposited up to a thickness of 10 nm without oxygen by evaporation method under following conditions:
  • the substrate temperature is adjusted at 570° C. and a second thin film of oxide superconductor of Y 1 Ba 2 Cu 3 O 7-x (3) having a thickness of 200 nm is deposited on the resulting thin film of Ag by off-axis sputtering under the same operational conditions as Example 1.
  • Example 3 also, three-layered thin films of a bottom superconductor layer of Y 1 Ba 2 Cu 3 O 7-x , an intermediate MgO layer and a top superconductor layer of Y 1 Ba 2 Cu 3 O 7-x are deposited successively on a substrate of MgO(100) by the condition (2) of the process according to the present invention whose steps are illustrated in FIG. 1.
  • a substrate (5) MgO (100) is placed in a ultra-high vacuum chamber which is then evacuated to 1 ⁇ 10 -9 Torr.
  • Substrate temperature 700° C.
  • the substrate temperature is lowered to 400° C. in order that oxygen is adsorbed in oxide superconductor.
  • the substrate temperature is lowered down to 370° C. and the ultra-high vacuum chamber is again evacuated to 1 ⁇ 10 -9 Torr. At the temperature of 370° C., oxygen do not escape out of the oxide superconductor.
  • a thin film of oxide superconductor of Y 1 Ba 2 Cu 3 O 7-x (3) having a thickness of 200 nm is deposited on the resulting thin film of MgO (2).
  • Deposition of this top superconductor layer (3) can be effected by any method. For example, in the case of off-axis sputtering, following operational conditions can be used:
  • Substrate temperature 700° C.
  • Example 3 is repeated but the MgO thin film is replaced by a thin film of Ag of the same thickness.
  • the substrate temperature is elevated to 700° C. and a second thin film of oxide superconductor of Y 1 Ba 2 Cu 3 O 7-x (3) having a thickness of 200 nm is deposited on the resulting thin film of Ag by off-axis sputtering under the same operational conditions as Example 1.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Superconductor Devices And Manufacturing Methods Thereof (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US08/457,313 1991-03-28 1995-06-01 Process for preparing a layered superconducting structure Expired - Fee Related US5629268A (en)

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US08/457,313 US5629268A (en) 1991-03-28 1995-06-01 Process for preparing a layered superconducting structure

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP3-089620 1991-03-28
JP3089621A JP2773456B2 (ja) 1991-03-28 1991-03-28 積層膜の作製方法
JP3-089621 1991-03-28
JP3089620A JP2773455B2 (ja) 1991-03-28 1991-03-28 積層膜の作製方法
US85842092A 1992-03-27 1992-03-27
US26130994A 1994-06-16 1994-06-16
US08/457,313 US5629268A (en) 1991-03-28 1995-06-01 Process for preparing a layered superconducting structure

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EP (1) EP0506582B1 (fr)
CA (1) CA2064428A1 (fr)
DE (1) DE69219941T2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022832A (en) * 1997-09-23 2000-02-08 American Superconductor Corporation Low vacuum vapor process for producing superconductor articles with epitaxial layers
US6027564A (en) * 1997-09-23 2000-02-22 American Superconductor Corporation Low vacuum vapor process for producing epitaxial layers
US6428635B1 (en) 1997-10-01 2002-08-06 American Superconductor Corporation Substrates for superconductors
US6458223B1 (en) 1997-10-01 2002-10-01 American Superconductor Corporation Alloy materials
US6475311B1 (en) 1999-03-31 2002-11-05 American Superconductor Corporation Alloy materials
KR100382754B1 (ko) * 1996-10-31 2003-07-22 삼성전자주식회사 메모리 소자
US20050077627A1 (en) * 2003-10-10 2005-04-14 Chen-Hua Yu Copper wiring with high temperature superconductor (HTS) layer
CN1364321B (zh) * 1999-07-23 2010-06-02 美国超导体公司 多层制品及其制造方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5527766A (en) * 1993-12-13 1996-06-18 Superconductor Technologies, Inc. Method for epitaxial lift-off for oxide films utilizing superconductor release layers
US6436317B1 (en) 1999-05-28 2002-08-20 American Superconductor Corporation Oxide bronze compositions and textured articles manufactured in accordance therewith
US6562761B1 (en) 2000-02-09 2003-05-13 American Superconductor Corporation Coated conductor thick film precursor
US6974501B1 (en) 1999-11-18 2005-12-13 American Superconductor Corporation Multi-layer articles and methods of making same
US20020056401A1 (en) 2000-10-23 2002-05-16 Rupich Martin W. Precursor solutions and methods of using same

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EP0366949A1 (fr) * 1988-10-03 1990-05-09 Matsushita Electric Industrial Co., Ltd. Dispositif Josephson et procédé de sa fabrication
US5061687A (en) * 1988-11-29 1991-10-29 Ube Industries, Ltd. Laminated film and method for producing the same
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JPH116481A (ja) * 1997-06-17 1999-01-12 Ishikawajima Harima Heavy Ind Co Ltd ポンプの起動停止制御方法

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EP0366949A1 (fr) * 1988-10-03 1990-05-09 Matsushita Electric Industrial Co., Ltd. Dispositif Josephson et procédé de sa fabrication
US5061687A (en) * 1988-11-29 1991-10-29 Ube Industries, Ltd. Laminated film and method for producing the same
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JPH116481A (ja) * 1997-06-17 1999-01-12 Ishikawajima Harima Heavy Ind Co Ltd ポンプの起動停止制御方法

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100382754B1 (ko) * 1996-10-31 2003-07-22 삼성전자주식회사 메모리 소자
US6022832A (en) * 1997-09-23 2000-02-08 American Superconductor Corporation Low vacuum vapor process for producing superconductor articles with epitaxial layers
US6027564A (en) * 1997-09-23 2000-02-22 American Superconductor Corporation Low vacuum vapor process for producing epitaxial layers
US6426320B1 (en) 1997-09-23 2002-07-30 American Superconductors Corporation Low vacuum vapor process for producing superconductor articles with epitaxial layers
US6428635B1 (en) 1997-10-01 2002-08-06 American Superconductor Corporation Substrates for superconductors
US6458223B1 (en) 1997-10-01 2002-10-01 American Superconductor Corporation Alloy materials
US6475311B1 (en) 1999-03-31 2002-11-05 American Superconductor Corporation Alloy materials
CN1364321B (zh) * 1999-07-23 2010-06-02 美国超导体公司 多层制品及其制造方法
US20050077627A1 (en) * 2003-10-10 2005-04-14 Chen-Hua Yu Copper wiring with high temperature superconductor (HTS) layer
US7105928B2 (en) 2003-10-10 2006-09-12 Taiwan Semiconductor Manufacturing Company, Ltd. Copper wiring with high temperature superconductor (HTS) layer

Also Published As

Publication number Publication date
DE69219941D1 (de) 1997-07-03
EP0506582A3 (en) 1993-01-27
EP0506582A2 (fr) 1992-09-30
EP0506582B1 (fr) 1997-05-28
CA2064428A1 (fr) 1992-09-29
DE69219941T2 (de) 1997-11-20

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